JP5726977B2 - Automotive interior parts with reduced squeaking noise - Google Patents

Description

  The present invention relates to an automobile interior part, and more particularly, to an automobile interior part made of a thermoplastic resin composition containing an aliphatic polyester-based resin, which greatly reduces the squeaking noise generated by contacting and rubbing with other parts. .

  ABS resin is widely used in the manufacture of automotive interior parts due to its excellent mechanical properties, heat resistance, moldability and the like.

  However, due to vibrations during automobile travel, ABS resin automobile interior parts come into contact with each other and with other parts such as chloroprene rubber, polyurethane, natural rubber, polyester or polyethylene lining sheets and foam. In the case of rubbing, it may generate a squeaking sound (friction sound). For example, a ventilator made of ABS resin is equipped with a valve shutter that uses chloroprene rubber foam or the like as a sealing material to adjust the air volume, and seals when the valve shutter is rotated to adjust the air volume. The wood and the ventilator case rub against each other. As described above, a squeaking noise may be generated even under a use situation in which an ABS resin automobile interior part rubs against other parts.

  In addition, since ABS resin and ASA resin are amorphous resins, they have a higher coefficient of friction compared to crystalline resins such as polyethylene, polypropylene, and polyacetal, and are used for air conditioner outlets and car stereo buttons in automobiles. As described above, it is well known that a stick-slip phenomenon (Non-Patent Document 1) occurs and abnormal noise (stagnation sound) occurs when mated with a component made of another resin. These squeaking noises are a major cause of impairing comfort and quietness when riding, and reduction of squeaking noises has been strongly desired.

  Therefore, in order to prevent these squeaking noises, a method of applying Teflon (registered trademark) coating to the surface of the component, a method of mounting Teflon (registered trademark) tape, a method of applying silicone oil, etc. have been performed. The process such as coating is not only complicated and time-consuming, but also has a problem that the effect is not sustained when placed under high temperature.

  Further, as a method for modifying the material itself used for automobile interior parts, for example, a technique (Patent Document 1) in which an organosilicon compound is blended with a resin made of polycarbonate resin and ABS resin, flame retardant, difficult A technology for blending a fuel aid and silicone oil (Patent Document 2), a technology for blending silicone oil in ABS resin, MBS resin and HIPS (High Impact Polystyrene) resin (Patent Document 3), and alkane in ABS resin A technique for blending a sulfonate surfactant (Patent Document 4) further blends ABS resin with a modified polyorganosiloxane having at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group, Disclosed is a technology (Patent Document 5) that is used for water-related parts in bathrooms and toilets. To have.

  However, the effect of reducing stagnation noise by these methods is not sufficient, and even if it shows a certain level of stagnation noise prevention effect immediately after molding, the effect is not long-lasting, especially when placed at high temperatures for a long time Had a problem that the effect was reduced.

Japanese Patent Publication No. 63-56267 Japanese Patent No. 2798396 Japanese Patent No. 2688619 Japanese Patent No. 2659467 JP 10-316833 A

Surface Science Vol.24, No.6, P328-333,2003.

In view of such circumstances, the present invention significantly reduces the squeaking noise generated when the parts rub against each other, and maintains the squeaking noise reduction effect even when left under high temperature for a long time. The purpose of the present invention is to provide automobile interior parts that are excellent in surface properties and molded article surface appearance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formulated a thermoplastic resin composition containing a specific aliphatic polyether resin and a specific thermoplastic resin, and a specific additive added thereto. It has been found that the occurrence of squeaking noise is remarkably reduced by the thermoplastic resin composition, and that the squeaking noise reduction effect is maintained without deteriorating even when placed at a high temperature for a long time. It came.

That is, according to the present invention, an automobile interior part having the following characteristics is provided.
1. It consists of a thermoplastic resin composition obtained by blending 5 to 300 parts by mass of the following thermoplastic resin (B) with 100 parts by mass of the following aliphatic polyester resin (A), and further comprising the thermoplastic resin composition Automotive interior parts characterized by blending 5 to 150 parts by mass of the following block copolymer (C) with respect to 100 parts by mass:
(A) an aliphatic polyester-based resin having, as a repeating unit, a unit formed from an aliphatic diol and / or an alicyclic diol and a unit formed from an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid,
(B) a styrene resin obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence or absence of the rubbery polymer (a) ,
(C) A block copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound, and at least one block copolymer selected from hydrogenated products thereof.
2. 2. The automotive interior part according to 1 above, wherein the aliphatic polyester resin (A) has a glass transition temperature (Tg) of 0 ° C. or lower and a melting point (Tm) of 130 ° C. or lower.
3. To 100 parts by mass of the thermoplastic resin composition described in 1 or 2 above, at least one polyethylene resin (D) selected from low molecular weight oxidized polyethylene, ultrahigh molecular weight polyethylene, and polytetrafluoroethylene is added in an amount of 0.001. An automobile interior part comprising a thermoplastic resin composition blended with 1 to 30 parts by mass.
4). An automobile interior comprising a thermoplastic resin composition obtained by blending 0.1 to 8 parts by mass of silicone oil (E) with respect to 100 parts by mass of the thermoplastic resin composition according to 1 or 2 above. parts.
5. 5. The automobile interior part as described in any one of 1 to 4 above, which is used for an automobile ventilator.
6). 5. The automobile interior part according to any one of 1 to 4 above, which is used for an air conditioner for an automobile.

  According to the present invention, a thermoplastic resin composition containing a specific aliphatic polyether resin and a specific thermoplastic resin is excellent in impact resistance and surface appearance of a molded product, and squeaking noise generated when parts are rubbed together. Is significantly reduced, and an automobile interior part that does not deteriorate the effect of reducing squeaking noise even when placed at a high temperature for a long time can be obtained.

Hereinafter, the present invention will be described in detail.
In the present specification, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acryl and / or methacryl.

  The aliphatic polyester resin as component (A) of the present invention is formed from a unit formed from an aliphatic diol and / or an alicyclic diol and an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid as a repeating unit. Unit.

  The above diol can be represented by the following general formula (1).

In the general formula (1), R1 represents a divalent aliphatic hydrocarbon group. As carbon number of R1, it is 2-11 normally, Preferably it is 2-6. R1 may include a cycloalkylene group or may have a branched chain. R1 is preferably - a "(CH ₂₎ n-" Here, n is an integer of 2 to 11, preferably an integer of 2-6.

  Specific examples of the diol include ethylene glycol, trimethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, Examples include 1,6-cyclohexanedimethanol. Among these, 1,4-butanediol is preferable from the viewpoint of reducing squeaking noise. The above diols may be used alone or in combination of two or more.

  Said dicarboxylic acid can be represented by the following general formula (2).

In the general formula (2), R2 represents a direct bond or a divalent aliphatic hydrocarbon group. Carbon number of R2 is 2-11 normally, Preferably it is 2-6. R2 includes a cycloalkylene group and may have a branched chain. R2 is preferably “— (CH ₂ ) m—”, where m is 0 or an integer of 1 to 11, preferably 0 or 6.

  Specific examples of the dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, dodecanedioic acid, and derivatives thereof. The derivatives include these lower alkyl esters and acid anhydrides. As the derivative, a compound in which both of two carboxy groups are converted into, for example, an ester group is preferable. Among these, succinic acid or adipic acid is preferable, and succinic acid is particularly preferable from the viewpoint of reducing the squeaking noise of the resulting aliphatic polyester. The above carboxylic acids may be used alone or in combination of two or more.

  The aliphatic polyester-based resin (A) can be copolymerized with a bifunctional aliphatic oxycarboxylic acid and a trifunctional aliphatic oxycarboxylic acid.

  The bifunctional aliphatic oxycarboxylic acid is not particularly limited as long as it has one hydroxyl group and one carboxylic acid group in the molecule, but the aliphatic oxycarboxylic acid represented by the following general formula (3) Acid is preferred.

  In general formula (3), R3 represents a divalent aliphatic hydrocarbon group. Carbon number of R3 is 1-11 normally, Preferably it is 1-16. R3 may include a cycloalkylene group or may have a branched chain.

  The bifunctional aliphatic oxycarboxylic acid is preferably a compound having a hydroxyl group and a carboxyl group at one carbon atom. In particular, the use of a compound represented by the following general formula (4) is preferred because the polymerization rate increases. .

  The bifunctional aliphatic oxycarboxylic acid is preferably a compound having a hydroxyl group and a carboxyl group at one carbon atom. In particular, the use of a compound represented by the following general formula (4) is preferred because the polymerization rate increases. .

  In general formula (4), z is 0 or an integer of 1 or more, preferably 0 or 1 to 10, and more preferably 0 or 1 to 5.

  Specific examples of the bifunctional aliphatic oxycarboxylic acid include lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-n-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy Examples include -3-methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid, and mixtures thereof. When optical isomers exist in these, any of D-form, L-form, and racemic form may be sufficient, and the shape may be any of solid, liquid, and aqueous solution. In particular, lactic acid or glycolic acid and an aqueous solution thereof are preferred because the increase in polymerization rate during use is remarkable and easy to obtain. Lactic acid and glycolic acid are generally commercially available as 50%, 70%, and 90% aqueous solutions, and are easily available.

  The trifunctional aliphatic oxycarboxylic acid includes a compound having three hydroxyl groups and carboxyl groups in total, that is, (a) a compound having two carboxyl groups and one hydroxyl group in the molecule, and (b) in the molecule. There are compounds having one carboxyl group and two hydroxyl groups. From the viewpoint of easy availability from the market and low cost, the above (a) is preferable. Further, those having a relatively low molecular weight are preferred, and specifically, malic acid is preferred.

  The aliphatic polyester-based resin (A) can be obtained by using the above-described components and reacting under the polyester forming conditions. Here, the polyester production conditions are: (a) ester bond formation by a simple dehydration reaction, (b) dealcoholation (ie transesterification) which is another condensation, and (c) addition when an acid anhydride is used. Means a condition that causes An azeotropic agent may be used to promote dehydration or dealcoholization, and reduced pressure conditions may be employed. In addition, a catalyst may be used.

  The proportion of the diol component used is substantially equimolar with respect to the dicarboxylic acid component (including derivatives), but it may be distilled during the esterification reaction in the actual production process. Usually, it is used in an excess of 1 to 20 mol%. The usage-amount of bifunctional aliphatic oxycarboxylic acid is 60 mol or less normally with respect to 100 mol of dicarboxylic acids, Preferably it is 0.04-20 mol, More preferably, it is 3-10 mol. With such a use amount, a higher molecular weight aliphatic polyester resin (A) can be obtained. The usage-amount of bifunctional aliphatic oxycarboxylic acid is 5 mol or less normally with respect to 100 mol of dicarboxylic acid components, Preferably it is 1 mol or less. If the amount used exceeds 5 moles, the risk of gelation during the reaction increases.

  The addition time of the bifunctional aliphatic oxycarboxylic acid is not particularly limited as long as it is before the polyester formation reaction, but (a) the raw material is charged or the esterification reaction is performed in a state where the catalyst is previously dissolved in the aliphatic oxycarboxylic acid solution. Or (b) a method in which a catalyst is added at the same time as starting materials is added.

  Examples of the catalyst used for the esterification reaction include metal compounds soluble in the reaction system such as germanium, titanium, antimony, tin, magnesium, calcium, and zinc. Among these, germanium compounds are preferable, and specific examples thereof include organic germanium compounds such as tetraalkoxygermanium, and inorganic germanium compounds such as germanium oxide and germanium chloride. Germanium oxide, tetraethoxygermanium or tetrabutoxygermanium is particularly preferred because of its price and availability.

  The usage-amount of a catalyst is 0.001-3 mass% normally with respect to the total amount of the monomer amount to be used, Preferably it is 0.005-1.5 mass%. The catalyst addition time is not particularly limited as long as it is before the production of the polyester, but it may be added when the raw materials are charged, or may be added at the start of pressure reduction. It is particularly preferable to add the bifunctional aliphatic oxycarboxylic acid at the same time as charging the raw material or to dissolve the catalyst in the bifunctional aliphatic oxycarboxylic acid and an aqueous solution thereof.

  The conditions such as the temperature, time, and pressure of the esterification reaction are not particularly limited as long as the target aliphatic polyester can be obtained, but the reaction temperature is usually 150 to 260 ° C, preferably 180 to 230 ° C. The reaction time is usually 1 hour or more, preferably 2 to 15 hours, and the reaction pressure is usually 10 mmHg or less, preferably 2 mmHg or less.

The number average molecular weight (Mn) of the aliphatic polyester-based resin (A) is usually 1 to 200,000, preferably 3 to 20 from the object of the present invention, squeaking noise reduction, impact resistance and molded article surface appearance. Ten thousand. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), Mw / Mn, is usually 3 or more, preferably 4 or more.
Moreover, it is preferable that the glass transition temperature (Tg) of aliphatic polyester-type resin (A) is 0 degrees C or less, and melting | fusing point (Tm) is 130 degrees C or less from a squeaking sound reduction property and impact resistance.

  At least one of the diol component and the dicarboxylic acid component constituting the aliphatic polyester resin (A) of the present invention may be derived from a plant, and both raw materials may be derived from a plant.

  As long as the effects of the present invention are not impaired, other copolymerization components can be introduced into the aliphatic polyether resin (A) of the present invention. Other copolymer components include aromatic oxycarboxylic acids such as hydroxybenzoic acid; aromatic diols such as bisphenol A; aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; trifunctional or higher aliphatic polyols, aliphatic Examples thereof include polycarboxylic acids and aromatic polycarboxylic acids; tetrafunctional or higher functional oxycarboxylic acids. The amount of these components used is usually 50 mol% or less, preferably 20 mol% or less, based on the total amount of monomers used.

The component (B) of the present invention includes a styrene resin (B-1), an olefin resin (B-2), a polylactic acid aliphatic polyester resin (B-3), and a polyacetal resin (B-4). It is at least one selected thermoplastic resin.
Here, as the styrene resin to be used (B-1) are aromatic Zokubi sulfonyl compound the presence or absence of a rubbery polymer (a), or an aromatic vinyl compound and aromatic vinyl compound and a co A polymer obtained by polymerizing a vinyl monomer (b) comprising another polymerizable vinyl monomer, and the vinyl monomer (b) is added in the presence of the rubbery polymer (a). Styrenic resin (B-1-X) obtained by graft polymerization and styrene resin (B-1-Y) obtained by polymerizing the vinyl monomer (b) in the absence of a rubbery polymer. ) Can be used alone or in combination of two or more.
The component (B-1) of the present invention is at least one kind of a polymer obtained by graft polymerization of a vinyl monomer (b) in the presence of the rubbery polymer (a) from the viewpoint of impact resistance and squeaking noise reduction. The thing containing is preferable. The content of the rubber polymer (a) is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, particularly preferably 10 to 60% by mass, with the component (B-1) being 100% by mass. is there.

The rubbery polymer (a) used in the styrene resin (B-1-X) is not particularly limited, but conjugated dienes such as polybutadiene, butadiene / styrene random copolymer, butadiene / acrylonitrile random copolymer, and the like. -Based rubber: ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / butene-1 copolymer, ethylene / α-olefin based ethylene / butene-1 / non-conjugated diene copolymer, etc. Examples of rubbers include acrylic rubber, silicone rubber, silicone / acrylic multilayer rubber, natural rubber, and the like. These may be used alone or in combination of two or more.
Among these, polybutadiene, butadiene / styrene random copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, acrylic rubber, silicone rubber and natural rubber are preferable, and polybutadiene and butadiene are more preferable. Styrene random copolymer, ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer and acrylic rubber.
Here, in the case of producing the component (B-1-X) using a solid rubber polymer, for example, an ethylene / propylene rubber polymer, it is necessary to emulsify the rubber polymer. As a method, a rubbery polymer described in JP-A-2002-265773 is dissolved in a solvent, an emulsifier, water and the like are added and stirred, and then the solvent is distilled off to obtain a rubbery polymer latex. A method of using a crosslinked rubber latex obtained by subjecting a polymer to a crosslinking reaction in the production of the component (B-1-X), and an extruder described in JP-A-2006-45467, a rubber polymer, an emulsifier, water Etc. are added and kneaded and then added to warm water to obtain a latex, and then a crosslinked rubber latex obtained by carrying out a crosslinking reaction on the rubbery polymer is used for the production of the component (B-1-X). .

As the rubbery polymer (a), one having a gel or one having no gel can be used. However, when (B-1-X) of the present invention is obtained by emulsion polymerization, the rubbery polymer (a) is resistant. From the viewpoint of impact properties, it is preferable to use one having a gel. The preferred gel content is usually 98% by mass or less, more preferably 20 to 98% by mass, and particularly preferably 40 to 98% by mass.
The gel content is determined at the time of production of the rubbery polymer (a). And a known method for appropriately setting the amount and the like. Moreover, the said gel content rate can be calculated | required by the method shown below.

  That is, 1 g of a rubbery polymer was put into 100 ml of toluene (but acetonitrile in the case of an acrylic rubbery polymer), allowed to stand for 48 hours at a temperature of 25 ° C., and then put between centrifugations. Centrifugation with a centrifuge (rotation speed: 22,000 rpm) for 1 hour, the insoluble matter obtained by separating the soluble and insoluble matter is dried for 6 hours with a vacuum dryer at 80 ° C. and weighed (mass W grams) And calculated by the following equation (5).

  Gel content (mass%) = [W / 1] × 100 (5)

A vinyl monomer comprising an aromatic vinyl compound in the presence or absence of the rubber polymer (a), or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound. The body (b) is polymerized to obtain the component (B-1) of the present invention.
As the aromatic vinyl compound used here, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, Examples include vinyl naphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

  Other vinyl monomers copolymerizable with aromatic vinyl compounds include vinyl cyanide compounds, (meth) acrylic acid esters, maleimide compounds, and carboxyl groups, acid anhydride groups, hydroxyl groups, amino groups, amide groups. There are functional group-containing unsaturated compounds having one or more functional groups such as an epoxy group and an oxazoline group, and these can be used alone or in combination of two or more.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  (Meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate Acrylates such as benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, methacrylic acid And methacrylic acid esters such as cyclohexyl, phenyl methacrylate, and benzyl methacrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate and butyl acrylate are preferred.

Examples of maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide. These can be used alone or in combination of two or more. Of these, N-cyclohexylmaleimide and N-phenylmaleimide are preferable.
As a method for introducing the monomer comprising the maleimide compound into the polymer, a method in which maleic anhydride is copolymerized in advance and then imidized is also preferably used.

  Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid, and these are used alone or in combination of two or more. be able to. Of these, acrylic acid and methacrylic acid are preferred.

  Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more. Of these, maleic anhydride is preferred.

  Examples of the hydroxyl group-containing unsaturated compound include hydroxystyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3- Examples include hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide, and these are used alone or in combination of two or more. can do. Of these, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

  Amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, propylaminoethyl methacrylate, Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylicamine, methacrylamine, N-methyl An acrylic amine etc. are mentioned, These can be used individually or in combination of 2 or more types.

  Examples of the amide group-containing unsaturated compound include acrylamide, N-methylacrylamide, methacrylamide, and N-methylmethacrylamide. These can be used alone or in combination of two or more. Of these, acrylamide is preferred.

  Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more. Among these, glycidyl methacrylate is preferable.

  Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these can be used alone or in combination of two or more.

The vinyl monomer (b) is preferably used in combination with the aromatic vinyl compound or the combination of the aromatic vinyl compound and the other vinyl monomer copolymerizable with the aromatic vinyl compound. Those are combinations of aromatic vinyl compounds and other vinyl monomers copolymerizable with aromatic vinyl compounds. More preferred combinations here are aromatic vinyl compounds / vinyl cyanide compounds, aromatic vinyl compounds / (meth) acrylic acid esters, aromatic vinyl compounds / vinyl cyanide compounds / (meth) acrylic acid esters, aromatic vinyl compounds. / Maleimide compounds, particularly preferably styrene / acrylonitrile (60-90 / 10-40; mass ratio), styrene / methyl methacrylate (10-90 / 10-90; mass ratio), styrene / phenylmaleimide (50- 95 / 5-50; mass ratio), α-methylstyrene / acrylonitrile / styrene (50-80 / 20-40 / 0-10; mass ratio), styrene / n-butyl acrylate / methyl methacrylate (0-40 / 5-30 / 30-95; mass ratio).
Here, the copolymer composed of an aromatic vinyl compound / maleimide compound includes those obtained by imidizing an acid anhydride of an aromatic vinyl compound / maleic anhydride copolymer with an amine compound (eg, aniline). It is. In that case, it may not be completely imidized and a part of acid anhydride groups may remain, but this is also included in the aromatic vinyl compound / maleimide compound copolymer.

  Moreover, when combining a functional group containing unsaturated compound with the above-mentioned preferable monomer combination, it is 0-30 mass% normally with respect to 100 mass% of monomers whole quantity, Preferably it is 0-20 mass%, Furthermore, Preferably it is 0-15 mass%.

  The component (B-1-X) of the present invention is a rubber-reinforced styrene resin obtained by graft polymerization of the vinyl monomer (b) in the presence of the rubber polymer (a). Here, usually, the (co) polymer of the monomer component (b) is grafted to the component (a), and the (b) component (b) not grafted to the component (a). Co) polymers are included. However, this graft copolymer may contain (a) component which (b) component (co) polymer is not grafted.

The component (B-1-X) of the present invention can be produced by a known polymerization method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and a combination thereof. In the production of a rubber-reinforced styrene resin, when a conjugated diene rubber or an acrylic rubber is used as the rubber polymer (a), a preferred polymer method is emulsion polymerization. On the other hand, when ethylene / α-olefin rubber is used, preferred polymerization methods are solution polymerization and bulk polymerization. In the presence of the solid polymer (a), the monomer component (b) may be added at once for polymerization, or may be divided or continuously added for polymerization. Further, the rubbery polymer (b) may be polymerized by adding the whole amount or a part thereof during the polymerization with the vinyl monomer.
Further, the styrene resin (B-1-Y), which is a (co) polymer obtained by polymerizing the vinyl monomer (b) in the absence of a rubbery polymer, is emulsion polymerization, solution polymerization, Either suspension polymerization or bulk polymer may be used, but solution polymerization, suspension polymerization and bulk polymerization are preferable from the viewpoint of productivity, and suspension polymerization and emulsion polymerization are preferable from the viewpoint of gel generated during production.

As the polymerization initiator, chain transfer agent, emulsifier and the like used in the various polymerization methods of the component (B-1) of the present invention, all known ones are used. Moreover, a well-known method is used also about polymerization conditions, such as superposition | polymerization temperature. Furthermore, all known methods can be used for the method of recovering the polymer after polymerization.
The volume average particle diameter of the rubber polymer (a) dispersed in (B-1-X) of the present invention is usually in the range of 50 to 3,000 nm, preferably 80 to 2,000 nm, more preferably. Is in the range of 80 to 1,000 nm, and in this range, the balance between the impact resistance and the surface appearance of the molded product is particularly excellent. These volume average particle diameters can be measured by an image analysis method or the like for measuring the diameter of dispersed particles observed with a transmission electron microscope.

  The graft ratio of the component (B-1-X) of the present invention is usually 10 to 150% by mass, preferably 20 to 120% by mass. Outside this range, the impact resistance may decrease.

The graft ratio can be determined by the following formula (6).
Graft ratio (mass%) = [(ST) / T] × 100 (6)

  In the above formula, 1 g of component (B-1-X) is added to 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then centrifuged under a temperature condition of 25 ° C. This is the mass (gram) of insoluble matter obtained by centrifuging for 60 minutes with a separator (rotation speed: 23,000 rpm) and separating the insoluble matter and the soluble matter, and T is (B-1-X) component 1 It is the mass (gram) of rubbery polymer contained in grams. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate or a method of obtaining from an infrared absorption spectrum (IR).

  Further, the acetone-soluble component of (B-1-X) and the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the component (B-1-Y) are both usually 0.1 to 1. 0.5 dl / g, preferably 0.2 to 1.0 dl / g. When the intrinsic viscosity [η] is in the above range, the physical property balance between molding processability and impact resistance is excellent. Here, the intrinsic viscosity can be adjusted by appropriately selecting the type and amount of chain transfer agent used during production, the type and amount of polymerization initiator, the polymerization temperature, and the like.

Examples of the olefin resin that is the component (B-2) of the present invention include (co) polymers comprising at least one olefin having 2 to 10 carbon atoms, and the olefin resin (B-2) is These can be used alone or in combination of two or more.
Examples of olefins used for forming the olefin resin (B-2) include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1. , Α-olefins such as 3-methylhexene-1, and cyclic olefins such as norbornene. These can be used alone or in combination of two or more. Of these, ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, and norbornene are preferable.
Other monomers that can be used as necessary in the formation of the olefin resin (B-2) include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 7-methyl. Non-conjugated dienes such as -1,6-octadiene, 1,9-decadiene and the like can be mentioned.

  As the olefin resin (B-2), a polymer mainly containing a propylene unit such as polypropylene and a propylene / ethylene copolymer, polyethylene, and an ethylene-norbornene copolymer are preferable, and these may be used alone or in combination of two or more. Can be used. Examples of the propylene / ethylene copolymer include random copolymers, block copolymers, metallocene polypropylene, and the like. As the polyethylene, any of high density polyethylene, low density polyethylene, linear low density polyethylene, metallocene polyethylene, and the like can be used.

As the olefin resin (B-2) of the present invention, those produced by a known polymerization method can be used, and examples thereof include a high pressure polymerization method, a low pressure polymerization method, and a metallocene catalyst polymerization method.
Furthermore, as the olefin resin used in the present invention, one obtained by removing the polymerization catalyst as a catalyst or one modified with an acid anhydride group, a carboxyl group, an epoxy group, or the like can be used.

It does not matter whether the olefin resin (B-2) has crystallinity, but it is preferable to use at least one of those having a crystallinity by X-ray diffraction of 10% or more at room temperature.
Moreover, it is preferable to use at least 1 sort (s) whose melting | fusing point measured based on JISK7121 of an olefin resin (B-2) is 40 degreeC or more.
When a polypropylene resin is used as the component (B-2) of the present invention, the melt flow rate measured according to JIS K7210: 1999 (230 ° C., load 2.16 kg) is preferably 0.01 to 500 g / 10. Min, more preferably 0.05 to 100 g / 10 min. When a polyethylene resin is used, the melt flow rate measured according to JIS K6922-2 (190 ° C., load 2.16 kg) is preferably 0.01 to 500 g / 10 min, more preferably 0.05 to 100 g / 10 min.

  What mixed | blended various additives, such as antioxidant, a heat stabilizer, and a lubricant, can be used for the olefin resin (B-2) of this invention. Depending on the application to be used, it may be preferable to use the component (B-2) that does not contain the various additives that are generated gas components from the molded product.

  By blending the olefin resin (B-2) of the present invention, it has the effect of reducing squeaking noise, but from the squeaking noise reducing property, preferably it contains a polyethylene resin and a polyethylene resin. In view of squeaking noise reduction, impact resistance, and molded product surface appearance, a combination of a polypropylene resin and a polyethylene resin is preferable, and a mass ratio of polypropylene resin / polyethylene resin is more preferably 50 to 95 / The combination is in the range of 5-50, particularly preferably 60-90 / 10-40.

  The polylactic acid aliphatic polyester resin (B-3) used in the present invention is a polylactic acid aliphatic polyester resin having a lactic acid unit content of 70 mol% or more. The number average molecular weight of the polylactic acid-based aliphatic polyester resin is usually 30,000 or more, preferably 100,000 or more, from the viewpoint of having sufficient strength, and the upper limit is usually 900,000. The molar ratio (L / D) of L-form and D-form of lactic acid is not limited, and all compositions from 100/0 to 0/100 can be used. When a thing with a high elasticity modulus is preferable, it is preferable that L body is 95% or more. The content of lactic acid units in the polylactic acid-based aliphatic polyester resin is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The method for producing polylactic acid is not particularly limited, and examples thereof include a ring-opening polymerization method via lactide and a direct polycondensation method of lactic acid.

  As the monomer unit other than lactic acid, any of the aliphatic diol units, aliphatic dicarboxylic acid units and aliphatic oxycarboxylic acid units described in the above-mentioned aliphatic polyester resin (A) is used. be able to.

  The polyacetal-based resin (B-4) used in the present invention is a polymer compound having an oxymethylene group (—OCH 2 —) as a main constituent unit, and a polyacetal homopolymer substantially consisting of repeating oxymethylene units, A typical example is a polyacetal copolymer having other comonomer units other than oxymethylene units, and basically has a linear molecular structure. Furthermore, a polyacetal copolymer having a branched structure or a crosslinked structure introduced by copolymerizing a branch-forming component or a crosslinking-forming component, a block copolymer or graft having a repeating unit of an oxymethylene group and another polymer unit There are copolymers. These polyacetal resins can be used alone or in combination of two or more. In particular, a combination of a linear polyacetal resin and a small amount of a branched or crosslinked polyacetal resin is one preferred example.

  In general, a polyacetal homopolymer is produced by polymerization of anhydrous formaldehyde or trioxane (a cyclic trimer of formaldehyde) and is usually stabilized against thermal decomposition by esterifying its terminal.

  In general, polyacetal copolymers are produced by copolymerizing formaldehyde or a cyclic oligomer of formaldehyde as the main monomer and a compound selected from cyclic ether or cyclic formal as a comonomer, and usually removing the unstable moiety at the end by hydrolysis. By doing so, it is stabilized against thermal decomposition. In general, trioxane which is a cyclic trimer of formaldehyde is used as the main monomer. In general, trioxane is obtained by reacting an aqueous formaldehyde solution in the presence of an acidic catalyst and then purifying it by a method such as distillation. As the trioxane, those which do not substantially contain impurities such as water, methanol and formic acid are preferable.

  The cyclic ether and cyclic formal which are comonomers include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, oxetane, tetrahydrofuran, trioxepane, 1,3-dioxane, 1,3-dioxolane, propylene glycol formal, diethylene glycol. Formal, triethylene glycol, 1,4-butadienediol formal, 1,6-hexanediol formal and the like can be mentioned.

  Further, the comonomer component capable of forming a branched structure or a crosslinked structure includes alkyl glycidyl ethers such as methyl glycidyl ether, ethylene glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and naphthyl glycidyl ether; ethylene glycol diglycidyl ether, Examples include alkylene such as triethylene glycol diglycidyl ether and butanediol diglycidyl ether, and polyalkylene glycol diglycidyl ether. These comonomers can be used alone or in combination of two or more.

  From the viewpoint of suppressing the generation of formaldehyde from the polyacetal resin to a lower level, a polyacetal copolymer is preferably used. In particular, trioxane (component I) and at least one compound selected from cyclic ether and cyclic formal (component II) are used as component I / component II = 99.9 / 0.1 to 80.0 / 20.0. Is preferably copolymerized at a ratio (mass ratio) of 99.5 / 0.5 to 90.0 / 10.0.

  Moreover, as a compound chosen from cyclic ether and cyclic formal, ethylene oxide, 1,3-dioxolane, 1,4-butanediol formal, and diethylene glycol formal are preferable.

  In general, the polyacetal copolymer as described above can be obtained by adding an appropriate amount of a molecular weight regulator and performing cationic polymerization using a cationic polymerization catalyst. Molecular weight regulators, cationic polymerization catalysts, polymerization methods, polymerization equipment, catalyst deactivation processing after polymerization, terminal stabilization processing methods for crude polyacetal copolymers obtained by polymerization are well-known in many literatures, Any of them can be used.

  The weight average molecular weight of the polyacetal-based resin is usually 10,000 to 400,000, and the melt index (measured at 190 ° C. under a load of 2.16 kg according to ASTM-D1238) as a fluidity index is usually 0.00. 1-100 g / 10 minutes, preferably 0.5-80 g / 10 minutes.

  As the component (B) of the present invention, the styrene resin (B-1), the olefin resin (B-2), the polylactic acid aliphatic polyester resin (B-3) and the polyacetal resin (B- One selected from 4) or two or more selected. Here, in the case of using two or more types in combination, the preferred combination is rubber reinforced styrene resin (B-1-X) / olefin resin (B-2), rubber reinforced from impact resistance and squeaking noise reduction. Rubber-reinforced styrene comprising styrene-based resin (B-1-X) / polylactic acid-based aliphatic polyester resin (B-3), rubber-reinforced styrene-based resin (B-1-X) / polyacetal-based resin (B-4) Containing resin (B-1-X). Further, the above-mentioned styrene resin (B-1-Y) obtained by polymerizing a vinyl monomer (b) in the absence of a rubbery polymer can be used in combination with a rubber-reinforced styrene resin as an essential component. . Here, the use ratio of the rubber-reinforced styrene resin (B-1-X) and the styrene resin (B-1-Y) / other resin used as necessary is 10 to 90/10 to 90 by mass ratio. Used in the range of

The component (B) of the present invention is used in the range of 5 to 300 parts by mass, preferably in the range of 10 to 250 parts by mass, with respect to 100 parts by mass of the aliphatic polyester resin (A) of the present invention. . Here, in the case of the styrene resin (B-1), it is more preferably 20 to 250 parts by mass, and particularly preferably 30 to 200 parts by mass. In the case of an olefin resin (B-2), it is more preferably 10 to 200 parts by mass, particularly preferably 10 to 100 parts by mass. In the case of the polylactic acid aliphatic polyester resin (B-3), the amount is more preferably 20 to 250 parts by mass, particularly preferably 50 to 250 parts by mass. In the case of the polyacetal resin (B-4), the amount is more preferably 10 to 150 parts by mass, and particularly preferably 10 to 100 parts by mass. Moreover, the more preferable range in the case of using (B) component combining the said 2 component or more is 20-250 mass parts, Most preferably, it is the range of 30-200 mass parts.
When the component (B) is blended, the balance between the squeaking noise reduction and the impact resistance can be further improved among the objects of the present invention. However, when the component (B) is out of the above range, the effect is insufficient, which is not preferable.

  The component (C) of the present invention comprises a block copolymer (C-a) having a polymer block (C-1) mainly comprising an aromatic vinyl compound and a polymer block (C-2) mainly comprising a conjugated diene compound. ) And a hydride thereof (Cb), at least one polymer selected from the group consisting of the component (A) and the component (B) of the present invention. Used for the purpose of improving impact resistance and squeaking noise reduction.

Examples of the aromatic vinyl compound used in the component (C) of the present invention include styrene, α-methylstyrene, hydroxystyrene, and the like, preferably styrene and α-methylstyrene, and particularly preferably styrene. Furthermore, the polymer block (C-1) may partially contain a conjugated diene compound.
Examples of the conjugated diene compound used here include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and preferably butadiene and isoprene. These can be used alone or in combination of two or more. Further, the polymer block (C-2) may be a block in which two or more kinds of conjugated diene compounds are used and bonded in a random, block, or tapered form. In addition, (C-2) may contain 1 to 10 taper blocks in which the aromatic vinyl compound and the aromatic compound gradually increase, and the conjugated diene compound of the polymer block (C-2) The derived polymer blocks having different vinyl bond contents may be appropriately copolymerized.

A preferred structure of the component (C) of the present invention is a polymer represented by the following formulas (I to III) or a hydride thereof.
(AB) Y (I)
(AB) YX (II)
A- (BA) Z (III)
In the structural formulas (I) to (III), A is a polymer block mainly composed of an aromatic vinyl compound. If the polymer block is substantially composed of an aromatic vinyl compound, a conjugated diene compound is partially included. It may be. The polymer block preferably contains 90% by mass or more, more preferably 99% by mass or more of the aromatic vinyl compound. B is a homopolymer of a conjugated diene compound or a copolymer of a conjugated diene compound with another monomer such as an aromatic vinyl compound, X is a residue of a coupling agent, and Y is 1-5. An integer and Z each represents an integer of 1 to 5. When B is a copolymer of another monomer such as an aromatic vinyl compound and a conjugated diene compound, the content of the other monomer in B is the conjugated diene compound and the other monomer. It is preferable that it is 50 mass% or less with respect to the sum total.

  In the component (C) of the present invention, the use ratio of the aromatic vinyl compound and the conjugated diene compound is preferably within the range of aromatic vinyl compound / conjugated diene compound = 10 to 80/20 to 90% by mass, more preferably 25 to 25%. It is 70 / 30-75 mass%, Most preferably, it is the range of 20-60 / 40-80 mass%. By being in the above range, the impact resistance, the molded product surface appearance and the squeaking noise reduction are particularly excellent.

  A block copolymer comprising an aromatic vinyl compound and a conjugated diene compound is known in the technical field of anionic polymerization. For example, Japanese Patent Publication No. 47-28915, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48- No. 2423, and Japanese Patent Publication No. 48-20038. A method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217.

  The vinyl bond content (1,2- and 3,4-bond) content derived from the conjugated diene compound of the component (C) of the present invention is preferably in the range of 5 to 80%. The number average molecular weight of the component is preferably 10,000 to 1,000,000, more preferably 20,000 to 500.000, and particularly preferably 20,000 to 200,000. Among these, the adjustment of the vinyl bond amount of the B part represented by the above (I) to (III) is N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, diazocyclo (2,2,2) octamine and the like. Amines, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and other ethers, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, potassium and sodium alkoxy, and the like.

  After obtaining the polymer by the above method, a polymer in which a polymer chain is extended or branched via a coupling agent residue using a coupling agent is also preferably included in the component (C) of the present invention. The coupling agent used here is diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2- Examples include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.

  In addition, as the component (C), the block copolymer itself can be used, or one obtained by partially or completely hydrogenating the carbon-carbon double bond of the conjugated diene moiety can be used. It is preferable to use a partially hydrogenated product and / or a completely hydrogenated product obtained by hydrogenating 50% or more from the impact resistance and the molded product surface appearance of the obtained composition.

  The hydrogenation reaction of the block copolymer containing the polymer block mainly composed of the aromatic vinyl compound obtained above and the polymer block mainly composed of the conjugated diene compound can be carried out by a known method, The target polymer can be obtained by adjusting the hydrogenation rate by a known method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, JP-A-1 There is a method disclosed in Japanese Patent No. 297413.

  The component (C) of the present invention is preferably used in an amount of 5 to 150 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition comprising the component (A) and the component (B). It is 5-100 mass parts, Most preferably, it is 10-80 mass parts. If it is less than 5 parts by mass, the effect of improving impact resistance and squeaking noise reduction is small, and if it exceeds 150 parts by mass, the impact resistance and the surface appearance of the molded product may be inferior.

  Further, the thermoplastic resin composition comprising the components (A) and (B) of the present invention, or the squeaking sound reducing property of the thermoplastic resin composition comprising the components (A), (B) and (C). For the purpose of further improvement, at least one polyethylene resin (D) selected from low molecular weight oxidized polyethylene, ultrahigh molecular weight polyethylene, and polytetrafluoroethylene can be blended.

  Here, the low molecular weight oxidized polyethylene has a number average molecular weight modified with a carboxylic acid group and / or an acid anhydride group (measured by GPC method) of 800 to 10,000, preferably 800 to 6,000, more preferably. 1,000 to 5,000, particularly preferably 1,200 to 4,000. The acid value representing the addition amount of the acid component is usually 1 to 40 (mg KOH / g), preferably 10 to 40 (mg KOH / g), more preferably 10 to 35 (mg KOH / g), and particularly preferably 10 ~ 30 (mg KOH). If the molecular weight is less than 800, the effect of improving the stagnation sound is reduced. On the other hand, if it exceeds 10,000, the impact resistance may be inferior. Further, if the acid value is less than 1, the effect of improving the squeaking noise is small, and if it exceeds 40, appearance defects such as silver streaks may occur at the time of molding, which is not preferable.

  Low molecular weight oxidized polyethylene is a known method, (1) a method in which low molecular weight polyethylene is oxidized in air to generate carboxylic acid groups, and (2) ethylene and carboxylic acid group-containing unsaturated compounds and / or acid anhydride groups. A method of copolymerizing the unsaturated compound, and (3) unsaturated by adding a carboxylic acid group-containing unsaturated compound and / or an acid anhydride group-containing unsaturated compound and an organic peroxide in the molten state of low molecular weight polyethylene. It can be produced by a method of adding a compound.

Such low molecular weight oxidized polyethylenes are Sun Wax E-310, E-330, E-250P, LEL-400P (EX) (all trade names), Umex (trade name) 2000, Clariant, manufactured by Sanyo Chemical Industries, Ltd. Commercially available products can be obtained as Recolum H12, H22 (all are trade names), Rico wax (trade name) PED521, PED522, PED153, PED191, PED821, and PED822 (all are trade names).
The low molecular weight acid value polyethylene of the present invention can be used alone or in combination of two or more.

  The ultra-high molecular weight polyethylene is polyethylene having an average molecular weight of 400,000 to 6.5 million measured by melt viscosity method in accordance with ASTM D4020, and a preferable average molecular weight is 400,000 to 3.5 million, more preferably 400,000 to 2.5 million. is there. Even when blended with the components (A) and (B) of the present invention and melt-kneaded, the ultrahigh molecular weight polyethylene of the present invention exists in an unmelted state. The average particle size measured by the counter method is preferably 50 μm or less, more preferably in the range of 5 to 40 μm.

Ultra high molecular weight polyethylene is Hi-Zex Million C30S, 145M, 240S, 240M, 320M, 340M, and 530M (all trade names) manufactured by Mitsui Chemicals, Inc. Mipelon (trade name) XM-220 with a smaller average particle diameter. XM-221U (both are trade names), etc., and are available as commercial products.
The ultra high molecular weight polyethylene of the present invention can be used alone or in combination of two or more.

Polytetrafluoroethylene is usually used as a dry lubricant. Preferably, it is in the form of fine powder, and the particle diameter of the fine powder is an average of 0.1 to 100 μm by a method of measuring a dispersion dispersed in perchlorethylene by a light transmission method. The melting point of the polytetrafluoroethylene fine powder is preferably 320 ° C. or higher by DSC measurement. Since the polytetrafluoroethylene fine powder is easily re-agglomerated, some of it has been subjected to a treatment such as a baking treatment in order to make it difficult to re-agglomerate, and these can be preferably used. Such polytetrafluoroethylenes are Daikin Industries' Lubron L-5 and L-2 (both trade names), Asahi IC Fluoropolymers L150J, L169J, L170J and L172J (all trade names), Mitsui A commercially available product can be obtained as Teflon (registered trademark) TLP-10F-1 (trade name) manufactured by DuPont Fluorochemicals.
The polytetrafluoroethylene resin of the present invention described above can be used alone or in combination of two or more.

  The low molecular weight oxidized polyethylene, ultrahigh molecular weight polyethylene and polytetrafluoroethylene which are the component (D) of the present invention can be used alone or in combination of two or more. A preferable combination when used in combination is a combination of low molecular weight oxidized polyethylene and polytetrafluoroethylene, or a combination of low molecular weight oxidized polyethylene and ultrahigh molecular weight polyethylene.

  These (D) components are usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition comprising the (A) component, (B) component and (C) component of the present invention, Preferably, it is used in the range of 0.2 to 25 parts by mass. Here, if it is less than 0.1 parts by mass, the effect of improving the squeaking noise reduction is small, and if it exceeds 30 parts by mass, the impact resistance and the surface appearance of the molded product are inferior.

Moreover, a silicone oil (E) can be mix | blended with the thermoplastic resin composition which consists of (A) component of this invention, (B) component, and (C) component from the objective of improving a squeaking noise reduction property. The silicone oil used here may be a known one as long as it has a polyorganosiloxane structure. These may be non-modified silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, etc., or may be a part of the side chain in the polyorganosiloxane structure and / or the polyorganosiloxane structure. It may be a modified silicone oil in which various organic groups are introduced into one terminal part or both terminal parts of the polyorganosiloxane structure. Examples of the modified silicone oil include alkyl modified silicone oil, polyether modified silicone oil, fluorine modified silicone oil, higher alkoxy modified silicone oil, higher fatty acid modified silicone oil, methyl styryl modified silicone oil, methyl chlorinated phenyl silicone oil, methyl hydro Gen silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, acrylic acid modified silicone oil, methacrylic acid modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, carbinol modified silicone oil, etc. are used. be able to.
These silicone oils can be used alone or in combination of two or more.

  The kinematic viscosity at 25 ° C. of the silicone oil (E) used in the present invention is preferably 60 to 500.000 cSt, more preferably 500 to 350,000 cSt, particularly preferably 1,000 to 200,000 cSt, and this range. Outside, the squeaking noise reduction is inferior. The kinematic viscosity of the silicone oil was measured with an Ubbelohde viscometer according to ASTM D445-46T (JIS8803 is acceptable).

  The amount of the silicone oil (E) component used is 0.1 to 8 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition comprising the components (A), (B) and (C) of the present invention. Preferably, it is 0.5-5 mass parts, More preferably, it is 2.5-3.5 mass parts. When the blending amount of the component (E) is less than 0.1 parts by mass, the effect of reducing the squeaking noise is inferior, and when it exceeds 8 parts by mass, the molded product surface appearance and impact resistance tend to be inferior. It may be difficult to melt and knead when producing the thermoplastic resin composition.

  If necessary, the thermoplastic resin composition of the present invention includes a lubricant, a nucleating agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, an anti-aging agent, a plasticizer, an antibacterial agent, and an antifungal agent. Various additives such as colorants (pigments, dyes, etc.) and antistatic agents can be contained within the range not impairing the object of the present invention.

  Moreover, a well-known inorganic or organic filler can be mix | blended with the thermoplastic resin composition of this invention. The filler used here is glass fiber, glass flake, glass fiber milled fiber, glass powder, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron, etc. Powder or fibrous material, carbon black, tin-coated titanium oxide, tin-coated silica, nickel-coated carbon fiber, talc, calcium carbonate, calcium carbonate whisker, wollastonite, mica, kaolin, montmorillonite, hextrite, zinc oxide whisker, titanium There are potassium acid whisker, aluminum borate whisker, plate aluminum, plate silica and organically treated smectite, aramid fiber, phenol resin, polyester fiber, etc., and these can be used alone or in combination of two or more. .

Furthermore, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treatment, sizing agent, etc. can be used. With known coupling agents, surface treatment agents, sizing agents, etc. It can be used after treatment, and known coupling agents include silane coupling agents, titanate coupling agents, aluminum coupling agents and the like.
The said inorganic or organic filler is normally used in 1-200 mass parts with respect to 100 mass parts of the thermoplastic resin composition of this invention.

  Furthermore, the thermoplastic resin composition of the present invention includes other polymers such as thermoplastic aromatic polyester resins, thermoplastic polyurethanes, polycarbonates, polyphenylene sulfides, polyamides, polyphenylene ethers, polyamide elastomers depending on the required performance. Polyester elastomers, polyolefin elastomers, polyurethane elastomers and the like can be appropriately blended.

  The thermoplastic resin composition of the present invention is prepared by mixing each component at a predetermined mixing ratio using a tumbler mixer, a Henschel mixer, etc. It can be produced by melt-kneading under suitable conditions using a mixer. A preferred kneading method is a method using an extruder. Furthermore, when each component is kneaded, each component may be kneaded in a lump or may be kneaded in multiple stages. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. Moreover, it is preferable to supply the fibrous material among the fillers from the middle of the extruder using an addition method such as a side feeder in order to prevent cutting during kneading. The melt kneading temperature is usually in the range of 180 to 300 ° C.

  The automobile interior part of the present invention is obtained by molding the thermoplastic resin composition. There is no limitation on the method for producing the automobile interior part of the present invention comprising the thermoplastic resin composition, and injection molding, injection compression molding, gas assist molding, press molding, calendar molding, T-die extrusion molding, profile extrusion molding. It can be produced by a known method such as film molding.

There are no particular limitations on the other members that come into contact with the automotive interior parts of the present invention. For example, thermoplastic resins, thermosetting resins, rubbers, organic materials, inorganic materials, metal materials containing the rubber-reinforced styrene resin of the present invention. Etc.
Here, examples of the thermoplastic resin include polyvinyl chloride, polyethylene, polypropylene, ABS resin, AES resin, ASA resin, polystyrene, impact-resistant polystyrene, ethylene-vinyl acetate copolymer, polyamide (PA), and polybutylene terephthalate. (PBT), polyethylene terephthalate, polycarbonate (PC), aliphatic polyester such as polylactic acid, PC and / or PBT / ABS resin, PC and / or PBT / AES resin, PA / ABS resin, PA / AES resin and the like. These can be used alone or in combination of two or more.

  Examples of the thermosetting resin include phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and thermosetting polyurethane. These can be used alone or in combination of two or more.

  As rubber, chloroprene rubber, polybutadiene rubber, ethylene / propylene rubber, styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer, styrene / isoprene block copolymer, hydrogenated styrene / isoprene system Examples include various synthetic rubbers such as block copolymers, natural rubber, and the like.

  Organic materials include, for example, insulation board, MDF (medium fiber board), hard board, particle board, lumbar core, LVL (single board laminate), OSB (orientation board), PSL (pararam), WB (wafer) Board), hard fiber board, soft fiber board, lumbar core plywood, special core-plywood, veneer core-veneer board, laminated sheet / board of paper impregnated with tap resin, (old) fine small pieces / wires crushed paper etc. The board which mixed the adhesive agent with the body and heat-compressed, various woods, etc. are mentioned.

Examples of the inorganic material include calcium silicate board, flexible board, homocement board, gypsum board, sizing gypsum board, gypsum lath board, decorative gypsum board, composite gypsum board, various ceramics, and glass.
Furthermore, iron, aluminum, copper, various alloys, etc. are mentioned as a metal material.
Among the above-mentioned other members that are in contact with the automobile interior part of the present invention, the thermoplastic resin, the thermosetting resin, and the rubber are preferable, and the effect of reducing the squeaking noise that is the object of the present invention is preferable. Preferably, it is a composition with ABS resin, AES resin, ASA resin, and PC.

  The automotive interior parts of the present invention can greatly reduce the squeaking noise caused by contacting and rubbing with parts made of other materials, such as door trim, door lining, pillar garnish, console, door pocket, ventilator Duct, air conditioner, meter visor, instrument panel upper garnish, instrument panel upper garnish, A / T indicator, on / off switch (slide part, slide plate), grill front defroster, grill side defroster, lid cluster, cover instroyer, masks (mask) Switch, mask radio, etc.), glove box, pockets (pocket deck, pocket card, etc.), steering wheel horn pad, etc. Among them, it can be suitably used as an automobile ventilator and an automobile air conditioner, and can be particularly suitably used as a plate-shaped blade, a bulk shutter, a louver, and the like of an automobile ventilator. It is suitable for a part having such a fitting part with another member.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the examples, parts and% are based on mass unless otherwise specified.

(1) Evaluation method:
Various measurements in Examples and Comparative Examples were based on the following methods.

(1-1) Itching sound evaluation-1
Using an injection molding machine “J-100E” (model name) manufactured by Nippon Steel Co., Ltd., the thermoplastic resin composition shown in Table 1 and PC / ABS resin “CK43” (trade name) manufactured by Technopolymer Co., Ltd. An ISO dumbbell test piece consisting of the above was injection molded at 140-230 ° C. Next, 5 ISO dumbbell test pieces made of the thermoplastic resin composition shown in Table 1 and 5 ISO dumbbell test pieces made of “CK43” were alternately overlapped, and the both ends were twisted by hand to generate a squeaking sound. The situation of occurrence was evaluated. Evaluation was performed 5 times, and determination was performed based on the following evaluation criteria.
(Double-circle): There was no generation | occurrence | production of a squeaking sound in all five evaluations.
O: The occurrence of itching was slight in all five evaluations.
(Triangle | delta): The case where generation | occurrence | production of a squeaking sound was remarkable was contained in five evaluations.
X: In all five evaluations, the generation of itching sound was significant.
(1-2) Itching sound evaluation-2:
The test piece obtained above was left in a gear oven at 80 ° C. for 400 hours. Using the test piece, the state of occurrence of itching was evaluated by the same method as in (1-1) Itching sound evaluation 1 above.

(1-3) Impact resistance:
Using the electric injection molding machine “Erject NEX30” (model) manufactured by Nissei Plastic Industry Co., Ltd., molding a specified molded article based on ISO 179, which is made of the thermoplastic resin composition shown in Table 1, at 140 to 230 ° C. Then, Charpy impact strength (KJ / m ² ) was measured.

(1-4) Molded product surface appearance:
A flat test piece of 80 mm × 55 mm × 1.6 mm was injection-molded at 140 to 230 ° C. using an electric injection molding machine “Erject NEX30” (model) manufactured by Nissei Plastic Industry Co., Ltd.
The surface of the test piece was visually observed and evaluated according to the following criteria.
◯: Good with no appearance defects such as flow marks.
Δ: There are some appearance defects such as flow marks.
X: Appearance defects such as a flow mark are remarkable and appearance is inferior.

(2) Component (A) The following aliphatic polyester resin was used.
A1: GSPlaAZ91T (trade name) manufactured by Mitsubishi Chemical Corporation
Aliphatic polyester resin mainly composed of succinic acid / 1.4-butanediol The glass transition temperature (Tg) is −32 ° C. and the melting point (Tm) is 110 ° C.

(3) (B) Component (3-1) Styrene resin (B-1)
(3-1-1) Production Example 1; Polymer B-1-X1 (conjugated diene rubbery polymer / styrene / acrylonitrile copolymer)
In a 7-liter glass flask equipped with a stirring blade, in a nitrogen stream, 120 parts of ion exchange water, 0.5 part of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, polybutadiene latex (average particle diameter 200 nm, Gel content 85%) 30 parts (solid content), butadiene / styrene random copolymer latex (average particle size 600 nm, gel content 60%, styrene content 25%) 10 parts (solid content), styrene 14.6 parts , 5.4 parts of acrylonitrile was added, and the temperature was raised with stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After polymerization for 1 hour, 50 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 29.2 parts of styrene, 10.8 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan, and cumene hydroperoxide 0.01 Part was added continuously over 3 hours and polymerization was continued for another hour. The polymer conversion rate at this time was 98%.
Thereafter, 0.2 part of 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) was added to complete the polymerization. The latex of polymer B-1-X1 was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain polymer B-1-X1. The graft ratio of this polymer B-1-X1 was 66%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.44 dl / g.

(3-2) Styrenic resin (B-1)
(3-1-2) Production Example 2; Polymer B-1-X2 (ethylene / propylene copolymer / styrene / acrylonitrile copolymer)
In a 20 liter stainless steel autoclave equipped with a ribbon stirring blade, 22 parts of ethylene / propylene rubber [ethylene / propylene = 78/22 (%), Mooney viscosity (ML _{1 + 4} , 100 ° C.) 20], styrene 55 Part, acrylonitrile 23 parts, tert-dodecyl mercaptan 0.5 part and toluene 110 parts, the internal temperature was raised to 75 ° C., and the contents of the autoclave were uniformly dissolved by stirring for 1 hour. Thereafter, after sufficiently purging with nitrogen, 0.45 part of tert-butylperoxyisopropyl monocarbonate was added, and after the internal temperature was further raised to 110 ° C., this temperature was maintained, The polymerization reaction was carried out at a stirring speed of 100 rpm. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave, Unreacted substances and solvent were distilled off by distillation, and further, volatile components were substantially devolatilized using a vented extruder with a screw diameter of 40 mm (cylinder temperature: 220 ° C., vacuum degree: 760 mmHg) to form a polymer B- 1-X2 was obtained. The graft ratio of the polymer B-1-2 was 70%, the intrinsic viscosity [η] of acetone-soluble matter was 0.47 dl / g, and the ethylene / propylene rubber content was 23%.

(3-3) (B-1) Component (3-1-3) Production Example 3; Ethylene / propylene rubber copolymer latex Ethylene / propylene / dicyclopentadiene rubber [ethylene / propylene / diethylene in a stainless steel container Cyclopentadiene = 75/20/5 (%)] After dissolving 100 parts in 566 parts of n-hexane, 10 parts of acid-modified polyethylene (High Wax 2203A) manufactured by Mitsui Chemicals, Inc. was added, and 4.5 parts of oleic acid was further added. Was added and completely dissolved. Separately, 0.6 parts of ethylene glycol was added to an aqueous solution in which 0.9 parts of potassium hydroxide was dissolved in 700 parts of water, and the mixture was kept at 60 ° C. And stirred. Next, part of the solvent and water was distilled off to obtain a latex having a particle size of 400 to 600 nm. To 100 parts of the rubber component, 1.5 parts of divinylbenzene and 1.0 part of di-tert-butylperoxytrimethylcyclohexane are added as a crosslinking agent to the latex, and reacted at 120 ° C. for 1 hour. -Propylene copolymer latex was obtained.

(3-1-4) Production Example 4; Polymer B-1-X3 (ethylene / propylene rubbery copolymer / styrene / acrylonitrile copolymer)
After replacing the stainless steel autoclave used in Production Example 2 with nitrogen, 50 parts (solid form) of the ethylene / propylene copolymer latex prepared in Production Example 3 in a nitrogen stream, 170 parts of water, 0.01% sodium hydroxide Part, 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate, and 0.2 parts of glucose were charged. Polymerization is carried out while continuously adding a solution comprising 8 parts of acrylonitrile, 22 parts of styrene, 0.05 part of tert-dodecyl mercaptan and 0.1 part of cumene hydroperoxide over 3 hours at a constant temperature of 80 ° C. Thereafter, the polymerization was continued for 1 hour while maintaining the polymerization temperature to obtain a latex of polymer B-1-3. The polymerization conversion rate of the obtained latex was 98%. To this latex, 0.2 part of 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) was added to complete the polymerization. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a polymer B-1-X3. The graft ratio of this polymer was 63%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.4 dl / g.

(3-4) (B-1) Component (3-1-4)) Production Example 4; Polymer B-1-Y1 (styrene / acrylonitrile copolymer)
Two stainless steel autoclaves having a ribbon wing with an internal volume of 30 liters were connected and purged with nitrogen, and then 73 parts of styrene, 27 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. A solution comprising 0.12 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator Was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C. The average residence time was 2.0 hours, and the polymer conversion rate was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator and polymerization initiator supplied by the pump provided in the second reaction vessel. The reaction vessel was fed. The polymerization temperature of the second reaction vessel was 130 ° C. The polymer conversion rate at the second reactive group was 75%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the intrinsic viscosity [η] 0.48 dl / g of polymer B-1-Y1 was obtained.

(3-2) Component (B-2) (3-2-1) As a polypropylene resin, the following product manufactured by Nippon Polypro Co., Ltd. was used.
B-2-1; Novatec PPBC6C (trade name)
Block type polypropylene, melt flow rate 2.5 g / 10 min (3-2-2) The following products manufactured by Nippon Polyethylene Co., Ltd. were used as polyethylene resins.
B-2-2; Novatec HDHJ560 (trade name)
High density polyethylene, melt flow rate 7g / 10min

(3-3) Component (B-3) The following were used as the polylactic acid-based aliphatic polyester.
B-3-1; LACEAH-100J (trade name) manufactured by Mitsui Chemicals, Inc.

(3-4) Component (B-4) The following were used as the polyacetal resin.
B-4-1; Duracon M90S (trade name) manufactured by Polyplastics Co., Ltd.

(4) C component The following were used as (C) component of this invention.
C1: Tuftec H1041 (trade name) manufactured by Asahi Kasei Chemicals
Completely hydrogenated styrene-butadiene-styrene block copolymer having a styrene / butadiene ratio of 30/70, melt flow rate of 5.0 g / 10 min [JIS K7
210 (Conforms to 230 ° C, load 2.16kgf)]

(5) (D) component The following were used as (D) component of this invention.
(5-1) Low molecular weight oxidized polyethylene D1; Sunwax EP-250P (trade name) manufactured by Sanyo Chemical Industries
Acid value 20 mgKOH / g, average molecular weight 2000

(6) Component (E) The following silicone oil was used.
E1; Shin-Etsu Silicone KF-96H-10,000 cSt
Dimethyl silicone oil, kinematic viscosity at 25 ° C. 10,000 cSt

Reference Examples 1-8, Examples 9-12, Comparative Example 1
Each component was mixed with a Henschel mixer at the blending ratio shown in Table 1, then melt-kneaded using a twin-screw extruder with a vent (manufactured by Nippon Steel Works, TEX44, barrel set temperature 140-230 ° C), and pelletized. did. After the obtained pellets were sufficiently dried, a test piece was formed by the above method using the pellet, and evaluated by the above method using the obtained test piece. The evaluation results are shown in Table 1.
As can be seen from Table 1, the thermoplastic resin compositions of the present invention represented by Examples 9 to 12 have reduced squeaking noise that is the object of the present invention, and furthermore, impact resistance and surface appearance of molded products. We provide molded products with a good balance.
On the other hand, Comparative Example 1 is an example in which an aliphatic polyester other than the aliphatic polyester of the component (A) of the present invention is used, and itching sound reduction (both itching sound evaluation-1 and itching sound evaluation-2) And the impact resistance is inferior.

  The automobile interior parts of the present invention are significantly reduced in the squeaking noise generated when the parts rub against each other, and are maintained without deteriorating the squeaking noise reduction effect even when placed at a high temperature for a long time. An automobile interior part made of a thermoplastic resin composition excellent in impact and molded product surface appearance can be provided, and can be suitably used for an automobile ventilator, an automobile air conditioner, and the like. In particular, it can be suitably used for a component having a fitting portion with another member.

Claims (6)

It consists of a thermoplastic resin composition obtained by blending 5 to 300 parts by mass of the following thermoplastic resin (B) with 100 parts by mass of the following aliphatic polyester resin (A), and further comprising the thermoplastic resin composition Automotive interior parts characterized by blending 5 to 150 parts by mass of the following block copolymer (C) with respect to 100 parts by mass:
(A) an aliphatic polyester-based resin having, as a repeating unit, a unit formed from an aliphatic diol and / or an alicyclic diol and a unit formed from an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid,
(B) a styrene resin obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence or absence of the rubbery polymer (a) ,
(C) A block copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound, and at least one block copolymer selected from hydrogenated products thereof.   The automotive interior part according to claim 1, wherein the aliphatic polyester resin (A) has a glass transition temperature (Tg) of 0 ° C or lower and a melting point (Tm) of 130 ° C or lower.   3. At least one polyethylene resin (D) selected from low molecular weight oxidized polyethylene, ultrahigh molecular weight polyethylene, and polytetrafluoroethylene is added to 100 parts by mass of the thermoplastic resin composition according to claim 1 or 2. An automobile interior part comprising a thermoplastic resin composition containing 1 to 30 parts by mass.   An automobile comprising a thermoplastic resin composition comprising 0.1 to 8 parts by mass of silicone oil (E) per 100 parts by mass of the thermoplastic resin composition according to claim 1 or 2. Interior parts.   The automobile interior part according to any one of claims 1 to 4, wherein the automobile interior part is used in an automobile ventilator.   The automotive interior part according to any one of claims 1 to 4, wherein the automotive interior part is used in an automotive air conditioner.